Food containing anhydrous crystals of maltitol and the whole crystalline hydrogenated starch hydrolisate

ABSTRACT

The present invention relates to anhydrous crystals of maltitol and the whole crystalline hydrogenated starch hydrolysate mixture solid containing the crystals, and processes for the production and use thereof.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application is a continuation of application Ser. No.640,782, filed August 14, 1984, now abandoned, which in turn was adivisional application of Ser. No. 511,762, filed July 7, 1983, nowabandoned, which in turn was a divisional application of Ser. No.321,311, filed November 13, 1981, now U.S. Pat. No. 4,408,041.

FIELD OF THE INVENTION

The present invention relates to anhydrous crystals of maltitol and thewhole hydrogenated starch hydrolysate mixture solid containing saidcrystals, and processes for the production and use thereof.

BACKGROUND OF THE INVENTION

Maltitol is, as described in Japan Patent Publication No. 13,699/72(MITSUHASHI et al.), obtained by reduction of maltose, and has asweetness which is close in quality to that of sucrose, and a sweeteningpower about 75% higher than that of sucrose.

Since maltitol is hardly absorbable and utilizable in the digestivesystem, and hardly fermentable by oral microorganisms, it has been usedas a sweetener for low-caloric, dietary, low-cariogenic and health foodsfor diabetics, obese persons and those who are conscious of theirhealth, including dental health.

However, since maltitol in dry solid form is extremely hygroscopic anddeliquescent, and difficult to prepare into powder, it has usually beenhandled only in the form of an aqueous solution; thus, its use has beenextremely restricted. For example, amorphous, substantially-anhydrouscandies can be obtained by boiling down an aqueous maltitol solution at180°-190° C., but the candies must be stored in a moisture proof vesseltogether with desiccant due to their high hygroscopicity anddeliquescence; thus, the handling of such candies renders greatdifficulties.

As to the hygroscopic properties of maltitol, M. J. Wolfrom et al. havereported in J. Am. Chem. Soc., Vol. 62, pp. 2553-2555 (1940), thatmaltitol had been obtained only in the form of an amorphous, white,hygroscopic solid; and J. E. Hodge et al. have reported in CerealScience Today, Vol. 17, No. 7, pp. 180-188 (1972) that they had not yetobtained a non-hygroscopic solid form of maltitol and that maltitolcould be crystallized as a hygroscopic ethanol complex.

As obvious from the above descriptions, only a highly hygroscopicmaltitol solid has been hitherto known.

Recently, many attempts to reduce the high hygroscopicity of maltitol asmuch as possible, and also to obtain a maltitol in powder form have beenreported. For example, Japan Kokai No. 477/74 (UENO, Kunio et al.) and87,619/74 (HIDAKA, Yoshio et al.) disclose processes for the productionof maltitol powder by admixing a hydrophilic polymer, such as an ediblepolymer, to an aqueous maltitol solution, and drying up the mixture toobtain the objective powder. Japan kokai No. 59,312/75 (HISANO, Kazuakiet al.) discloses a process for the production of maltitol powder whichcomprises mixing a composition containing maltitol with a small amountof one or more members of mono-saccharides or their sugar alcoholderivatives, melting the mixture by heating to anhydrous fusion form,cooling the resultant, and spray-drying and fluidizing in a moistureproof tower to obtain the objective maltitol powder. Japan Kokai No.110,620/74 (HIRAIWA, Takashi), 24,206/75 (HIRAIWA, Takashi et al.),25,514/75 (OYAMADA, Ko-ichiro et al.), 32,745/76 (HIRAIWA, Takashi),106,766/76 (HIRAIWA, Takashi), 113,813/76 (HIRAIWA, Takashi), 128,441/76(HIRAIWA, Takashi) and 47,928/77 (HIRAIWA, Takashi) disclose processesfor the production of maltitol powder which comprise pulverizingmaltitol solids, under dried air conditions, and coating the resultantmaltitol powder with other edible powders. Japan Kokai No. 29,510/75(KANE-EDA, Jun et al.) discloses a method for preventing consolidationof powder containing maltitol wherein a powder containing maltitol ismoistened with a solvent which substantially dissolves maltitol, and isthen dried together with another sugar micro-powder, under mixingconditions, in order to apply a coating of the micro-powder on theparticles of maltitol powder.

All attempts have proved, however, unsuccessful because maltitol must bemixed with a large amount of other substance(s) or coated therewith, andthe high hygroscopicity of maltitol cannot be eliminated thereby. Ineffect, the maltitol powder obtained by any of the above describedprocesses or methods barely retains its powder form under ambientconditions, and still exhibits its high hygroscopicity; therefore, it isreadily susceptible to moisture-absorption, consolidation and/ordeliquescence under ambient conditions within a short time, and is notutilizable for practical uses.

SUMMARY OF THE INVENTION

The present inventors have investigated the properties of maltitol bothto overcome these disadvantages, and to obtain anhydrous crystals ofmaltitol and crystalline mixture solids, which have heretofore beenregarded as unattainable.

The respective wordings, "anhydrous crystals of maltitol" and"crystalline mixture solid," as used in the present specification andclaims, mean substantially-non- or low-hygroscopic maltitol crystalswhich can be a product of anhydrous crystals of maltitol with a highpurity, and a whole crystalline hydrogenated starch hydrolysate mixturesolid containing, besides anhydrous crystals of maltitol, other sugaralcohols, such as sorbitol, maltotriitol and maltotetraitol.

These efforts have resulted in the finding that maltitol crystals can beobtained as follows: A liquefied starch solution with a low DextroseEquivalent value (abbreviated as "DE" hereinafter), is subjected to theenzymatic actions of isoamylase (EC 3.2.1. 68) and β-amylase (EC3.2.1.2) to obtain a saccharified starch solution with a high maltosecontent, and the saccharified starch solution is then subjected topurification, concentration, crystallization and separation, obtaining acrystalline product with a maltose content of about 99% on dry solidbasis (all "percentages" used hereinafter mean "percentages on dry solidbasis" unless specified otherwise). Thereafter, an aqueous solution ofthe product is hydrogenated in the presence of Raney nickel catalyst,obtaining a maltitol solution with a high maltitol content up to about98.5%. The maltitol solution is concentrated to 75%, and subjected to anabout six-month standing from 35° to 5° C. in a soft-glass vessel toeffect crystallization. Then, the crystals grown on the vessel wall areadded as seed crystals to an 80% aqueous maltitol solution with the highmaltitol content, and the admixture is then subjected to crystallizationunder gentle stirring conditions, obtaining a mascuite which is thenseparated into mother liquor and maltitol crystals. The crystals arewashed by spraying a small amount of water, and recrystallized similarlyas above after dissolution in water, obtaining maltitol crystals with amuch higher purity.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an infrared spectrum of anhydrous crystals of maltitol;

FIG. 2 is an infrared spectrum of amorphous anhydrous maltitol;

FIG. 3 is a microphotograph of anhydrous crystals of maltitol, ×150;

FIG. 4 is a microphotograph of anhydrous crystals of maltitol, ×600; and

FIG. 5 is a stereo-scopic ORTEP figure of maltitol single crystal.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

The physical and chemical investigations on the crystals have led to thefinding that the crystals are anhydrous crystals of maltitol which havebeen hitherto unknown.

The physical and chemical properties of the anhydrous crystals ofmaltitol are as follows:

(1) Elemental analysis: C, 41.9%; H, 7.1%, and O, 51.0% (Found); C,41.86%, H, 7.03%; and O, 51.11% (Calculated) for C₁₂ H₂₄ O₁₁

(2) Molecular weight: 344.3

(3) Melting point: 146.5°-147.0° C.

(4) Specific rotation: [α]_(D) ²⁰, +106.5° (0.1 g per cc water)

(5) Ultraviolet absorption: no characteristic absorption is observedwhen dissolved in water

(6) Infrared absorption:

(a) Infrared spectrum of anhydrous crystals of maltitol; 5 mg anhydrouscrystals of maltitol in powder form and 220 mg KBr were mixed, andpressed into a transparent tablet, about 0.6 mm thick, which was thensubjected to infrared spectrometry (FIG. 1)

(b) Infrared spectrum of amorphous, anhydrous maltitol; 3 mg anhydrouscrystals of maltitol and 220 mg KBr were dissolved in hot water, and themixture was dried, and pressed into a transparent tablet, about 0.8 mmthick, which was then subjected to infrared spectrometry (FIG. 2)

(7) Solubility: 100 g water dissolves up to 165 g anhydrous crystals ofmaltitol at 25° C.

(8) Heat of dissolution: upon dissolution of 1 mole anhydrous crystalsof maltitol in 190 mole water at 15° C., 5.5 Kcal is endothermicallyabsorbed

(9) Appearances and properties: colorless, odorless, transparentcrystals (micro-crystals in lump white); no hygroscopicity anddeliquescence are observed; weight reduction upon heating at 130° C. fortwo hours is 0.5% or less; an aqueous solution of anhydrous crystals ofmaltitol is neutral or weakly acidic; and sweet tasting. FIGS. 3 and 4are microphotographs of anhydrous crystals of maltitol grown from anaqueous maltitol solution.

(10) Solubility in various solvents: readily soluble in water, 0.1N NaOHand 0.1N HCl; soluble in methanol and ethanol; and insoluble inchloroform and ethyl acetate

(11) color reaction: anthrone-sulfuric acid reaction, green; Fehlingreduction reaction, negative; and I₂ -test, negative

(12) Sugar components:

(a) Acid hydrolysis using 1N sulfuric acid, and subsequent paper andgas-liquid chromtographic analyses confirmed the presence of equimolarD-glucose and D-sorbitol fractions

(b) Complete methylation, hydrolysis and subsequent gas-liquidchromatographic analysis confirmed the presence of equimolar2,3,4,6-tetra-O-methyl-D-glucose and 1,2,3,5,6-penta-O-methyl-D-sorbitolfractions

(c) The high specific rotation, [α]_(D) ²⁰, of +106.5° and the infraredabsorption neighboring 840 cm⁻¹ suggest the presence of an α-linkagebetween the glucose and sorbitol moieties

(d) Paper, gas-liquid and high-pressure liquid chromatographic analyseson the anhydrous crystals of maltitol gave the same single spot or peakat the same position as in the analyses on a commercial authenticmaltitol preparation (special grade reagent)

(13) X-ray crystal structure: X-ray crystallographic study on a maltitolsingle crystal grown from a 75 w/w % supersaturated aqueous maltitolsolution at 40° C. gave the following crystal structure; ortho-rhombic,space group, P2₁ 2₁ 2₁ ; lattice constants, a=8.166 Å, b=12.721 Å,c=13.629 Å; and a stereoscopic ORTEP figure is given in FIG. 5.

The above-described physical and chemical properties of the maltitolcrystals led to the conclusion that the present crystals are hithertounknown anhydrous crystals of maltitol; neither sugar hydrate, such asβ-maltose mono-hydrate, nor the reported ethanol complex.

The following descriptions illustrate the process for the production ofanhydrous crystals of maltitol and crystalline mixture solid accordingto the present invention.

As to the maltitol solution which is subjected to crystallizationaccording to the present invention, any maltitol solution can be usedregardless of its production process so far as anhydrous crystals ofmaltitol can grow from the solution by the addition of seed crystals ata supersaturated concentration. Usually, an aqueous maltitol solution,prepared with a sugar alcohol mixture having a maltitol content at least65% to give a concentration, preferably, of 65-95% (super-saturationdegree of about 1.05-1.50), is subjected to crystallization at atemperature in the range of 0°-95° C., a range wherein freezing of thesolution does not occur, and wherein the heat loss is relatively low.

The supersaturation degree and viscosity of the solution can beregulated by the addition of water-soluble organic solvent, e.g.,methanol, ethanol or acetone.

Crystallization of the solution is usually started in a crystallizer ata relatively elevated temperature of about 40°-95° C. and asupersaturated concentration, and the content is simultaneously cooledgradually with gentle stirring down from the temperature to obtain amascuite containing anhydrous crystals of maltitol. In this case, thepresence of seed crystals in an amount of 0.1-20.0% can accelerate thecrystallization.

As described above, anhydrous crystals of maltitol can be easilycrystallized from a supersaturated aqueous maltitol solution by addingthereto a small amount of anhydrous crystals of maltitol or crystallinemixture solid as seed crystals.

The mascuite thus obtained can be separated into the anhydrous crystalsof maltitol and mother liquor by conventional separation method, orprepared into a crystalline mixture solid by a conventional total-sugarmethod such as block-pulverization, fluidized-bed granulation andspray-drying methods.

The former method usually comprises transferring the mascuite into abasket-type centrifugator, separating the mascuite into anhydrouscrystals of maltitol and mother liquor, and washing, if necessary, byspraying a small amount of chilled water thereto, obtaining anhydrouscrystals of maltitol with a much higher purity.

The total-sugar method does not augment the purity of maltitol, butrealizes a higher yield of crystalline mixture solid; thus, CRYSTALLINEMIXTURE SOLID obtained by any of the three methods inevitably contains,besides anhydrous crystals of maltitol, other sugar alcohols resultingfrom the starting material starch syrup as syrup constituents, such assorbitol, maltotriitol and maltotetraitol.

In spray-drying, a mascuite with a concentration of about 70-85%,wherein the crystallization has proceeded up to about 25-60%, isspray-dried via a nozzle, equipped at the top of a spray-drying tower,by a high-pressure pump at a temperature whereat the obtainedcrystalline powder does not melt, and which is maintained, for example,by charging a 60°-100° C. hot air. Thereafter, the crystalline powder isaged by supplying a 30°-60° C. air for about one to twenty hours toobtain a non- or substantially-non-hygroscopic crystalline mixturesolid.

The block-pulverization method usually comprises 0.5-5 day standing of amascuite with a moisture content of about 5-15%, wherein thecrystallization has proceeded up to about 10-60%, to solidify intoblocks which are then converted into powder by scraping, pulverizing andsubsequently drying.

In the latter total-sugar method, to a supersaturated solution in fusionform, prepared by concentration of an aqueous maltitol solution to amoisture content less than 5% by heating according to a conventionalmethod, can be added seed crystals, and the admixture is then kneaded ata temperature below its melting point, obtaining crystalline mixturesolid, followed by shaping of the resultant into a desirable shape,e.g., in the form of powder, granule, rod, plate or cube.

Although, dependent upon purity, the hygroscopicity of anhydrouscrystals of maltitol or crystalline mixture solid slightly varies, theyare substantially non-hygroscopic and free flowing; thus, they arefavorable for various uses, e.g., for producing foods, drinks,cosmetics, drugs and chemical materials, or preparing into desirableshapes, similar to granulated sucrose, without fear of sticking andconsolidation. Also, the physical properties of anhydrous crystals ofmaltitol and crystalline mixture solid, such as melting point andspecific rotation, vary according to their purities; with a decrease ofthe purity, the melting point declines and widens its range. Forexample, the melting point of crystalline mixture solid with a maltitolcontent of 85.2% is 120°-127° C. Accordingly, the purity of bothproducts can be selected freely to meet to the final uses.

Additionally, since, like sucrose, anhydrous crystals of maltitol andcrystalline mixture solid dissolve readily in the mouth, andendothermically absorb more heat, they exhibit a pleasant refreshingtaste; thus, they are desirable sweeteners.

Although anhydrous crystals of maltitol and crystalline mixture soliddissolve readily and quickly in water, they are substantiallynon-hygroscopic; thus, they are favorably feasible for sweeteningpowdered foods and drinks as described hereinafter.

Based on the above described features, the use of anhydrous crystals ofmaltitol or crystalline mixture solid easily enables industrial-scaleproduction of various foods and drinks, such as sweeteners in powder orsolid form, fondant, chocolate, chewing gum, powdered juice orconvenience soup; and shaped bodies, such as granules, or tablets, whichhave been impossible or very difficult to prepare with conventionalmaltitol. Furthermore, since anhydrous crystals of maltitol andcrystalline mixture solid are free flowing due to theirnon-hygroscopicity and low-susceptibility to consolidation, theeconomics realized by the reduction in labor, packing, transportationand storage costs therewith is beyond calculation.

Anhydrous crystals of maltitol and crystalline mixture solid are readilysoluble in water, satisfactorily heat- and acid-resistant, low-caloric,low-cariogenic and low-fermentable, and impart an appropriate sweetness,viscosity, body and gloss to foods and drinks, similar to conventionalmaltitol; thus, their superior properties make the production of foods,drinks, drugs and cosmetics more feasible.

The following descriptions explain the present invention in more detail.

Anhydrous crystals of maltitol and crystalline mixture solid can be usedas a sweetener without further processings, or, if necessary, incombination with other conventional sweeteners, e.g., starch syrupsolid, glucose, maltose, isomerized sugar, sucrose, honey, maple sugar,sorbitol, dihydrocharcone, stevioside, α-glycosyl stevioside, sweetextract from Momordica grosvenori, glycyrrhizin, L-asparatylphenylalanine methyl ester, saccharin, glycine and/or alanine; and/or incombination with fillers, e.g., dextrin, starch and/or lactose.

Also, they can be used intact, or mixed, if necessary, with filler,vehicle and/or binder, and then prepared into a desirable shape, e.g.,granule, globe, tablet, rod, plate or cube.

Since like conventional maltitol, they are hardly absorbable andutilizable by the digestive system, a sufficient calorie-reduction offoods and drinks can be realized therewith without changing theirdesirable properties; thus, they are favorably usable as a low-caloricsweetener, and for sweetening low-caloric foods and drinks, e.g.,dietary and health foods, for diabetics, obese persons and those whosecalorie-intakes are restricted.

Furthermore, since both products are hardly fermentable by dentalcaries-causative microorganisms, similarly as conventional maltitol,they can also be favorably used as a low-cariogenic sweetener forvarious confectionaries, e.g., chewing gum, chocolate, biscuit, cookie,caramel and candy; and soft drinks, e.g., cola drinks, cider, juice,coffee and yoghurt drinks. Also, they are favorably usable for reducingthe cariogenicities of cosmetics and drugs, such as gargle andtoothpaste, by replacing sucrose therewith, as well as for sweeteningthem.

The sweetness of anhydrous crystals of maltitol or crystalline mixturesolid well harmonizes with sour, salty, astringent, delicious and/orbitter tasting substance(s) as well as being highly acid- andheat-resistant; thus, in addition to the above described special uses,they are also favorably usable for sweetening foods and drinks ingeneral, and improving their taste qualities. For example, they may beused in seasonings such as sauce, soy sauce, soy sauce powder, soy saucepaste "MISO", soy sauce paste powder, mayonnaise, dressing, vinegar,vinegar powder, extracts for Chinese-style foods, catsup, curry roux,extracts for stew and soup, mixed seasonings and table and coffeesugars; confectionaries and bakery products such as Japanese-styleconfectionaries, jelly, castella, bread, biscuit, cracker, cookie, pie,pudding, butter cream, custard cream, choux cream, cream puff, waffle,sponge cake, doughnut, chocolate, chewing gum, caramel and candy; frozendesserts such as ice-cream and sherbet; syrups; pastes such as peanutpaste, flour paste and fruit paste; pickles and preserves such as jam,marmalade, preserves, processed vegetable and pickles; pickle additives;meat products such as ham and sausage; processed fish products;preserved foods; daily products such as cooked beans and potato salad;canned and bottled foods such as those of fish, meat, fruit, vegetableand shell; alcoholic drinks such as wine, whisky and brandy; soft drinkssuch as coffee, cocoa, juice, carbonated drinks, lactic acid drinks andyoghurt drinks; and convenience-type foods and drinks such as those ofpudding, hot cake, juice, coffee and soup.

Anhydrous crystals of maltitol and crystalline mixture solid arenon-hygroscopic and free flowing; thus, they are favorably usable forimproving the properties of pre-packed foods, and/or preventing thesticking and adhesion of the content on the package, for example, as inthe case of chewing gum.

Additionally, they are favorably feasible for improving the tastes ofpet foods or feeds for domestic animal or fowl, honey bee, silkworm orfish, as well as for sweetening and improving the tastes of tobacco,cosmetics and drugs which are in the form of solid, liquid or paste,such as toothpaste, lipstick, lipcream, drug for internaladministration, troche, cod-liver oil drop, cachou, gargle and oralrefreshing agent.

Anhydrous crystals of maltitol and crystalline mixture solid obtainedaccording to the present invention can be prepared into any desirableshape by spraying a small amount of water or an aqueous maltitolsolution thereon to slightly moisten them, and molding the resultantunder a slightly elevated pressure, as in the case of sucrose; forexample, in the shape of fish, animal, cube or flower. Thus, shapedsweetener for coffee or tea in any desirable shape can be easilyprepared to meet the final uses. To the shaped sweetener can be addedother sweeteners, e.g., α-glycosyl stevioside, sucrose and/or saccharinto further enhance the sweetness; coloring agent, for example, red orgreen; and/or flavor such as orange-, coffee- or brandy flavoring. Inflavoring, the objectives may be attainable with the use of aflavor-cyclodextrin complex (a host-guest complex).

Furthermore, since like sucrose they can be easily obtained in massiveform, they are favorably usable as a semi- or transparent sweetenersolid in place of the conventional candy sugar or coffee sugar.

Additionally, to anhydrous crystals of maltitol or crystalline mixturesolid other substances can be added freely, e.g., vitamin, antibioticsor microorganisms of genus Lactobacillus, prior to shaping, and theadmixture is then prepared into desirable shape, for example, a granulewith a granulizer, or a tablet with a tabletting machine.

As to the methods for incorporating anhydrous crystals of maltitol orcrystalline mixture solid into the above described foods, drinks,tobacco, pet foods, feeds, cosmetics, drugs or shaped bodies, anymethods can be employed in the invention so far as they are incorporatedtherein before the completion of processing. Preferable conventionalmethods are mixing, kneading, dissolving, dipping, melting, immersing,permeating, injecting, crystallizing and solidifying.

In addition to the above described uses, anhydrous crystals of maltitoland crystalline mixture solid are of low-moisture content orsubstantially anhydrous, and the small amount of moisture presenttherein can be removed completely by brief drying with hot air; thus,they can be favorably used in chemical reaction under anhydrousconditions. For example, etherification or esterification reaction ofanhydrous crystals of maltitol or crystalline mixture solid underanhydrous conditions leads to a higher yield of ether or esterderivative of maltitol. The derivatives thus obtained can be favorablyused, for example, as an emulsifier or surface-active agent.

Several embodiments of the present invention are disclosed hereinafter.

EXAMPLE 1 Seed Crystal

To a starch suspension, consisting of one part of potato starch and tenparts of water, was added a commercial liquefying α-amylase, and themixture was heated to 90° C. to effect gelatinization. The enzymaticliquefaction was suspended by immediately heating to 130° C., obtaininga liquefied starch solution with DE of about 0.5.

After cooling immediately the solution to 55° C., to the solution wasadded Pseudomonas amyloderamosa (ATCC 21262) isoamylase (EC 3.2.1.68) inan amount of 100 units per g starch, and a soy bean β-amylase "#1500"(Nagase & Company, Ltd., Osaka, Japan) in an amount of 50 units per gstarch, and the mixture was saccharified at this temperature and pH 5.0for 40 hours, obtaining a saccharified starch solution with a highmaltose content: glucose, 0.4%; maltose, 92.5%; maltotriose, 5.0%; andhigher oligosaccharides including maltotetraose, 2.1%.

The saccharified starch solution was purified by decolorization withactivated carbon, and deionization with ion exchangers.

After concentrating the purified saccharified starch solution to 75%,the concentrate was transferred into a crystallizer, and β-maltosemono-hydrate was added thereto as seed crystals in an amount of 1%. Theresultant admixture was then cooled gradually from 40° C. to 30° C. overa period of two days, followed by separation of the resultant mascuitewith a basket-type centrifuge into crystalline maltose and motherliquor. The crystalline maltose was washed by spraying with a smallamount of water, obtaining a highly-purified maltose with a purity of99.0%.

A 50% aqueous solution of the highly-purified maltose was placed in anautoclave, and added with Raney nickel catalyst in an amount of 10%.Thereafter, the content was heated to 90°-125° C., and hydrogenation waseffected at the temperature and a hydrogen pressure of 20-100 kg/cm².After completion of the hydrogenation, the Raney nickel catalyst wasremoved, and the residual aqueous solution was purified bydecolorization with activated carbon, and deionization with ionexchangers according to conventional methods, obtaining ahighly-purified maltitol solution with a purity of 98.5%.

After concentrating the highly-purified maltitol solution to 75% under areduced pressure, a small portion of the concentrate was placed in asoft-glass vessel, and allowed to stand at 30°-5° C. for about sixmonths to effect crystallization, resulting in the growth of theanhydrous crystals of maltitol on the vessel wall.

To an 80% aqueous maltitol solution was added the anhydrous crystals ofmaltitol as seed crystals, and the mixture was crystallized under gentlestirring conditions. The resultant mascuite was then transferred into abasket-type centrifugator, and separated therein into crystals andmother liquor. The crystals were then washed by spraying with a smallamount of water, obtaining highly-purified anhydrous crystals ofmaltitol with a purity of 99.8%.

The anhydrous crystals of maltitol have the following physicalproperties: melting point, 146.5°-147.0° C.; 100 g water dissolves up to165 g anhydrous crystals of maltitol at 25° C.; and no hygroscopicity isobserved under ambient conditions.

The anhydrous crystals of maltitol are favorably usable as seed crystalsin the production of additional anhydrous crystals of maltitol orcrystalline mixture solid.

EXAMPLE 2 Anhydrous Crystals of Maltitol

To a starch suspension, consisting of one part of potato starch and tenparts of water, was added a commercial Bacillus liquefying α-amylase,and the mixture was heated to 90° C. to effect gelatinization. Theenzymatic liquefaction was suspended immediately by heating the mixtureto 130° C., obtaining a liquefied starch solution with a DE of about0.5. The solution was then immediately cooled to 50° C., and added withan Escherichia intermedia (ATCC 21073) pullulanase (EC 3.2.1.41) in anamount of 50 units per g starch, and a soy bean β-amylase "#1500"(Nagase & Company, Ltd., Osaka, Japan) in an amount of 30 units per gstarch. The enzymatic saccharification was continued at this temperatureand pH 6.0 for 46 hours, and the saccharified starch solution wasdecolorized with activated carbon, and subsequently deionized with ionexchangers, obtaining a maltose solution with a sugar composition ofglucose, 0.4%, maltose, 92.5%, maltotriose, 4.8%, and higheroligosaccharides including maltotetraose, 2.3%, in the yield of about97% against the starting starch material.

After adjusting the concentration of the maltose solution to 50%, to theconcentrate was added Raney nickel catalyst in an amount of 10%, and theadmixture was then heated to 90°-125° C. under stirring conditions, andhydrogenated at this temperature under a hydrogen pressure of 20-100kg/cm². After completion of the hydrogenation, the Raney nickel catalystwas removed, and the hydrogenated product was purified with activatedcarbon and ion exchangers according to conventional methods, obtaining asugar alcohol mixture with a composition of sorbitol, 0.8%, maltitol,92.2%, maltotriitol, 4.6%, and higher sugar alcohols includingmaltotetraitol, 2.4%, in the yield of about 92% against the startingstarch material.

After concentrating the mixture to 80%, the concentrate was thentransferred into a crystallizer, added with anhydrous crystals ofmaltitol in powder form as seed crystals in an amount of 1%, and cooledgradually from 50° C. to 20° C. over a period of three days understirring conditions. The resultant mascuite was separated with abasket-type centrifugator into crystals and mother liquor. The crystalswere washed by spraying with a small amount of water, obtaining thetitled product with a maltitol content of 99.2% in the yield of about46% against the starting starch material.

The melting point of the product was 146.5°-147.0° C.

The product is highly pure and non-hygroscopic; thus, it is favorablyusable as a chemical material as well as sweetener and/ortaste-improving agent for various foods, drinks, cosmetics and drugs.

EXAMPLE 3 Crystalline Mixture Solid

To a starch suspension, consisting of three parts of corn starch and tenparts of water, was added a commercial Bacillus liquefying α-amylase,and the mixture was heated to 90° C. to effect gelatinization. Theenzymatic liquefaction was suspended by heating immediately the mixtureto 130° C., obtaining a liquefied starch solution with a DE of about 3.

After cooling immediately the solution to 55° C., to the solution wasadded Pseudomonas amyloderamosa (ATCC 21262) isoamylase (EC 3.2.1.68) inan amount of 100 units per g starch, and a soy bean β-amylase "#1500"(Nagase & Company, Ltd., Osaka, Japan) in an amount of 30 units per gstarch, and the mixture was kept at this temperature and pH 5.0 for 36hours to effect enzymatic saccharification. The saccharified starchsolution was purified similarly as in EXAMPLE 2, obtaining a maltosesolution with a sugar composition of glucose, 2.6%, maltose, 85.4%,maltotriose, 7.4%, and higher oligosaccharides including maltotetraose,4.6%.

Then, the hydrogenation of the maltose solution was carried outsimilarly as in EXAMPLE 2, obtaining a sugar alcohol mixture with acomposition of sorbitol, 3.6%, maltitol, 85.4%, maltotriitol, 6.8%, andhigher sugar alcohols including maltotetraitol, 4.6%.

Thereafter, the mixture was concentrated to 88%, and the concentrate wastransferred into a crystallizer, added with anhydrous crystals ofmaltitol in powder form as seed crystals in an amount of 2%, and kept at50° C. for two hours under gentle stirring conditions. The content wasthen placed in plastic vessels where it was allowed to stand at 20° C.for 4 days to effect solidification. The obtained blocks were removedfrom the vessels, and pulverized by a crusher equipped with a scraper.The resultant was dried to obtain the titled product in the yield of 90%against the starting starch material.

The melting point of the product is 120°-127° C.

The product is substantially non-hygroscopic and readily handleable:thus, it is favorably usable for improving the tastes of various foods,drinks, cosmetics and drugs as well as sweetening them.

EXAMPLE 4 Crystalline Mixture Solid

After concentrating a sugar alcohol mixture, obtained similarly as inEXAMPLE 2, to 80%, the concentrate was then transferred into acrystallizer, and added with crystalline mixture solid in powder form asseed crystals in an amount of 2%. The admixture was cooled graduallyfrom 50° C. with gentle stirring, obtaining a mascuite wherein thecrystallization had proceeded up to 35%. The mascuite was thenspray-dried via a 1.5 mm nozzle, equipped at the top of a sprayingtower, with a high-pressure pump at a pressure of 150 kg/cm².Simultaneously, 85° C. hot air was charged downwards from the top of thetower to collect the pulverized product on a net conveyer placed at thebottom of the tower, and to fluidize the product out of the tower over aperiod of 40 minutes while charging 40° C. air upwards through the net.The resultant was then transferred into an aging tower, and aged thereinfor ten hours to effect complete crystallization and drying, obtainingthe titled product in the yield of about 92% against the starting starchmaterial.

The product is non-hygroscopic and readily handleable; thus, it isfavorably usable in various chemical materials as well as in sweeteners.

EXAMPLE 5 Fondant

A starch suspension, consisting of five parts of corn starch and tenparts of water, was liquefied similarly as in EXAMPLE 3, obtaining aliquefied starch solution with DE of 5.

After cooling immediately the solution to 55° C., to the solution wasadded the isoamylase in an amount of 70 units per g starch and theβ-amylase in an amount of 10 units per g starch, and the mixture waskept at this temperature and pH 5.0 for 36 hours to effect enzymaticsaccharification. The resultant was then purified similarly as inEXAMPLE 2 to obtain a saccharified starch solution with a sugarcomposition of glucose, 0.9%, maltose, 77.6%, maltotriose, 12.5%, andhigher oligosaccharides including maltotetraose, 9.0%.

The solution was then hydrogenated similarly as in EXAMPLE 2, obtaininga sugar alcohol mixture with a composition of sorbitol, 1.4%, maltitol,77.3%, maltotriitol, 12.3%, and higher sugar alcohols includingmaltotetraitol, 9.0%.

After concentration of the mixture to 85%, the concentrate wastransferred into a crystallizer, added with seed crystals in an amountof 1%, and then cooled to ambient temperature under vigorous stirringconditions to effect crystallization. To the resultant was admixedanhydrous crystals of maltitol, obtained similarly as in EXAMPLE 2, toobtain the titled product.

The product is a white paste with a smooth and mild sweetness; thus, itis favorably usable as a material for various confectionaries.

EXAMPLE 6 Sweetener

A mixed sweetener was prepared by mixing homogenously one part ofcrystalline mixture solid in powder form, obtained similarly as inEXAMPLE 3, and 0.05 parts of a commercial α-glycosyl stevioside"α-G-Sweet" (Toyo Sugar Refining Co., Ltd., Tokyo, Japan).

The mixed sweetener has an excellent sweetness which is about two-foldhigher in sweetening power than that of sucrose, but the calorie-contentis about one-twentieth of that of sucrose; thus, the sweetener isfavorably usable for various low-caloric foods and drinks for diabetics,obses persons and those whose calorie-intakes are restricted.Additionally, since neither acid- nor water-insoluble glucan formationby dental caries causative-microorganisms is observed, it is favorablyusable for sweetening various low-cariogenic foods and drinks.

EXAMPLE 7 Cube Maltitol

One part of anhydrous crystals of maltitol, obtained similarly as inEXAMPLE 2, and 0.01 part of saccharin were mixed to homogeneity. Aftermoistening the mixture by spraying thereonto a small amount of anaqueous maltitol solution, the resultant was formed into cubes usingmolds for conventional cubic sugar under a relatively elevated pressure,and the cubes were removed from the molds, obtaining the titled product.

The product is a white, non-hygroscopic cube with sufficient physicalstrength and about two-fold higher sweetening power in comparison withthat of sucrose as well as being readily soluble in cold water; thus, itis an ideal low-caloric and low-cariogenic sweetener.

EXAMPLE 8 Cream wafers

A creamy product, prepared by mechanical mixing of a mixture, consistingof 2,000 parts of crystalline mixture solid in powder form, obtainedsimilarly as in EXAMPLE 3, 1000 parts of shortening, one part oflecithin, one part of lemon oil and one part of vanilla oil, accordingto conventional methods, was kept at 40°-45° C., and sandwiched betweenwafers to obtain the titled product.

EXAMPLE 9 Custard cream

Five hundred parts of corn starch, 500 parts of crystalline mixturesolid in powder form, obtained similarly as in EXAMPLE 4, 400 parts ofmaltose and 5 parts of NaCl were sufficiently mixed by shifting andsieving, and the mixture was added with 1,400 parts of egg, followed bystirring. Then, the mixture was gradually added with 5,000 parts ofboiling milk while stirring and heating the content on a slow-fire, andthe heating was suspended when the corn starch gelatinized and thecontent became transparent. Then, to the cooled content was furtheradded a small amount of vanilla flavor to obtain the titled product.

The product is a smooth, glossy and very delicious custard cream with noexcessive sweetness.

EXAMPLE 10 Chocolate

A mixture, consisting of 40 parts of cacao base, 10 parts of cacaobutter and 50 parts of anhydrous crystals of maltitol, obtainedsimilarly as in EXAMPLE 2, was placed in a refiner to reduce itsviscosity. Then, the content was transferred into a conche, and kneadedsufficiently therein at 50° C. for two days.

During the kneading step, 0.5 parts of lecithin was added thereto anddispersed sufficiently.

Thereafter, the content was charged at 30° C. under thermally-regulatedconditions into molds just before its solidification. The content wasdegassed by vibration, and solidified by passing through a 10° C.cooling tunnel for 20 minutes. The contents were then removed, andpacked to obtain the titled product.

The product is a non-hygroscopic chocolate with a mild and elegantflavor, excellent color and satisfactory brightness and texture, andmelts smoothly in the mouth, thus, it is an ideal low-cariogenic andlow-caloric chocolate.

EXAMPLE 11 Chocolate coated candy

A mixture, consisting of 95 parts of crystalline mixture solid in powderform, obtained similarly as in EXAMPLE 3, 5 parts of corn syrup and asmall amount of water, was homogenized by stirring to fluid state. Then,to the mixture was added small amounts of flavor and coloring agent, andthe admixture was poured with a depositor into molds in layered starch,and solidified partially therein. The flour starch attached thereon wasremoved by shifting and sieving to obtain the centers for the titledproduct. The centers were coated with an unsolidified chocolate,obtained similarly as in EXAMPLE 10, cooled, solidified, and finallypacked to obtain the titled product.

EXAMPLE 12 Chewing gum

Twenty-five parts of gum base and 40 parts of a fondant, obtainedsimilarly as in EXAMPLE 5, were kneaded at 60° C. by a mechanical mixer.To the mixture was added 30 parts of anhydrous crystals of maltitol,obtained similarly as in EXAMPLE 2, 1.5 parts of calcium phosphate, 0.1part of L-methol-β-cyclodextrin complex (a host-guest complex), andsmall amounts of condiments, and the admixture was then kneadedsufficiently, rolled and cut according to conventional methods to obtainthe titled product.

The product is an ideal low-cariogenic chewing gum.

EXAMPLE 13 Juice powder

Thirty-eight parts of juice powder, obtained by spray-drying, was addedwith 60 parts of crystalline mixture solid in powder form, obtainedsimilarly as in EXAMPLE 4, 0.65 parts of citric anhydride, 0.1 part ofmalic acid, 0.1 part of ascorbic acid, 0.1 part of sodium citrate, 0.6parts of a flavor powder and 0.5 parts of pullulan, and the mixture waskneaded sufficiently.

Then, the mixture was granulated in a fluidized-bed granulizer whereinthe mixture was first moistened by spraying thereon a 50% aqueousmaltitol solution, obtained similarly as in EXAMPLE 3, at a rate of 100ml per minute, and then fluidized into powder over a period of 30minutes by charging 40° C. air at a rate of 150 m³ per minute.

The product thus obtained is a powdered juice with a powdered orangejuice content of about 30%, and is free from unpleasant odor and tasteas well as being stable over the long period of storage withoutconsolidation.

EXAMPLE 14 Convenience potage soup

A mixture, consisting of 30 parts of gelatinized corn powder, 5 parts ofgelatinized wheat flour, 4 parts of gelatinized potato starch, 12 partsof gelatinized waxy corn starch, 8 parts of crystalline mixture solid inpowder form, obtained similarly as in EXAMPLE 3, 5 parts of sodiumglutamate, 8.5 parts of NaCl, 7 parts of defatted milk and 0.5 parts ofonion powder, was crushed and mixed sufficiently. The mixture was thenfurther added with 0.5 parts of a melted sorbitan aliphatic acid ester,9 parts of a melted hydrogenated vegetable oil and 10 parts of lactose,and the admixture was mixed sufficiently.

The admixture was granulated similarly as in EXAMPLE 13 in afluidized-bed granulizer wherein the admixture was sprayed with a smallamount of water, fluidized, and dried by 70° C. hot air. Thereafter, theresultant was shifted and sieved to obtain the titled product.

An addition of hot water to the product readily dissolves and dispersesthe product to give instantly a potage soup with an excellent flavor.

EXAMPLE 15 Extract of "UIRO"

A mixture, consisting of 90 parts of rice flour, 20 parts of cornstarch, 120 parts of crystalline mixture solid in powder form, obtainedsimilarly as in EXAMPLE 4, and 4 parts of pullulan, was kneaded tohomogeneity to obtain the titled product, "Extract of UIRO" - a type ofJapanese-style rice paste confectionaries.

Two hundred g of the extract and 1 g green tea powder ("MACCHA") wereadded with water, and the mixture was kneaded sufficiently. Then, theresultant was placed in a vessel, and steamed therein for 60 minutes toobtain a "MACCHA UIRO".

The product is excellent in gloss, flavor and biting properties. Also,the retrogradation of the amylaceous components is sufficientlysuppressed, and therefore the product is stable over a long period ofstorage.

EXAMPLE 16 Pickle additive for "BETTARA-ZUKE"

Four parts of crystalline mixture solid in powder form, obtainedsimilarly as in EXAMPLE 3, 0.05 parts of sweet extract from Licorice,0.008 parts of malic acid, 0.07 parts of sodium glutamate, 0.03 parts ofpotassium sorbate and 0.2 parts of pullulan were mixed and kneaded tohomogeneity, obtaining the titled "Pickle additive for BETTARA-ZUKE" - atype of Japanese-style pickles.

According to conventional methods, 30 kg of Japanese radish ("DAIKON",Raphanus sativus) was partially pickled with NaCl, and then furtherpickled with sucrose. The final pickling was carried out in a seasoningsolution, prepared with 4 kg of the additive, to obtain "BETTARA-ZUKE".

The product is moderately sweet, and excellent in color, brightness,flavor and biting properties. Also, the product is stable over a longperiod of storage due to its low susceptibility to excessivefermentation.

EXAMPLE 17 Tablet

Fifty parts of acetyl-salicylic acid, 14 parts of crystalline mixturesolid in powder form, obtained similarly as in EXAMPLE 3, and 4 parts ofcorn starch powder were mixed and kneaded sufficiently. Then, themixture was tabletted, 5.25 mm thick and 680 mg, using a conventionaltabletting machine.

The product is very moisture-resistant, and its physical strength isextremely high as well as being readily soluble in water.

EXAMPLE 18 Polyether derivative of maltitol

Three parts of anhydrous crystals of maltitol, obtained similarly as inEXAMPLE 2, and 0.2 parts of pyridine were placed together in a reactionvessel. The mixture was added with 3 parts of dimethyl sulfoxide, andpropylene oxide gas was then charged therein, while keeping the reactiontemperature at 90°-100° C. The reaction was suspended when about fiveparts of propylene oxide was consumed.

The solvents and residual reagent were removed by distillation at 120°C. and a reduced pressure of about 10-20 mm Hg under nitrogenatmosphere. The residue was cooled to about 60° C., added gradually withabout 5 parts of conc. hydrochloric acid with stirring, and furtheradded with 5 parts of benzene to form salts which were then removed byfiltration in vacuo. All benzene, water and hydrochloric acid wereremoved from the filtrate by distillation to obtain about 8 parts ofviscous oily polyether derivative of maltitol.

The derivative exhibits an excellent surface-active action: thus, it isfavorably usable in various uses, such as emulsifier, thickener ormoisture-retaining agent, as well as surface-active agent for generaluses.

In addition to the above described uses, it is favorably usable as amaterial in polyurethane production using isocyanate compounds.

EXAMPLE 19 Fatty acid ester derivative of maltitol

Two parts of crystalline mixture solid in powder form, obtainedsimilarly as in EXAMPLE 3, was dissolved in 7 parts of dimethylformamide. To the solution was added 0.6 parts of methyl palmitate and0.04 parts of potassium carbonate, and the mixture was subjected toester-exchange reaction overnight at a pressure of about 100-200 mm Hgand a temperature of about 80°-100° C. with sufficient stirring.

After completion of the reaction, the solvent was removed bydistillation in vacuo, and the residue was washed twice with three partsof acetone. After concentration of the residue, the concentrate waswashed with benzene and petroleum ether. The viscous oily product wasimmersed in three parts of acetone while heating, and the extract wasallowed to stand under ice-chilling conditions, obtaining a precipitatewhich was then treated with acetone, and dried to obtain 0.6 parts ofmaltitol mono-palmitate.

The derivative exhibits a satisfactory surface-active action; thus, itis favorably usable as an emulsifier for foods as well as an ingredientfor detergents.

What we claim is:
 1. In a process for producing a food-stuff whichcontains substantially non-hygroscopic, free-flowing sweetenercomprising incorporating said sweetener into the foodstuff, theimprovement wherein said substantially non-hygroscopic, free-flowingsweetener is selected from the group consisting of anhydrous crystals ofmaltitol and a whole crystalline hydrogenated starch hydrolysate mixturesolid containing anhydrous crystals of maltitol.
 2. A process inaccordance with claim 1, wherein said foodstuff is in solid form.
 3. Aprocess in accordance with claim 1, wherein said foodstuff is in finelydivided form.
 4. A process in accordance with claim 1, wherein saidfoodstuff is a sweetener.
 5. A process in accordance with claim 1,wherein said foodstuff is a sweetened, low-calorie foodstuff.
 6. Aprocess in accordance with claim 1, wherein said foodstuff is asweetened, low-cariogenic foodstuff.
 7. A process in accordance withclaim 1, wherein the maltitol incorporated into the foodstuff isanhydrous crystals of maltitol obtained by:providing a 40°-95° C.aqueous solution having a dry solids concentration of 65-95% by weightand a maltitol content of at least 65% based on the weight of the drysolids, wherein the saturation degree of said aqueous solution is in therange of 1.05-1.50; gradually cooling the solution and allowing thesolution to stand for a time sufficient to effect crystallization; andrecovering anhydrous crystals of maltitol from the resultant crystalsuspension.
 8. A process in accordance with claim 7, wherein thesolution is added with an effective amount of seed crystals.
 9. Aprocess in accordance with claim 8, wherein the amount of seed crystalsis in the range of 0.1-20.0% relative to the dry solids.
 10. A processin accordance with claim 8, wherein the solution is cooled understirring conditions.
 11. A process in accordance with claim 8, whereinthe recovering step comprises:separating the crystal suspension intoanhydrous crystals of maltitol and the mother liquor on a centrifuge;and washing the anhydrous crystals of maltitol with a minimum amount ofchilled water.
 12. A process in accordance with claim 8, wherein saidanhydrous crystals of maltitol are separated from the crystal suspensionwith a basket-type centrifuge.
 13. A process in accordance with claim 7,wherein said aqueous solution has been obtained by:catalyticallyhydrogenating maltose in aqueous solution; and purifying thehydrogenated solution.
 14. A process in accordance with claim 1, whereinthe maltitol incorporated into the foodstuff is whole crystallinehydrogenated starch hydrolysate mixture solid containing anhydrouscrystals of maltitol obtained by:providing a 40°-95° C. aqueous solutionhaving a dry solids concentration of 65-95% by weight and a maltitolcontent of at least 65% based on the weight of the dry solids, whereinthe saturation degree of said aqueous solution is in the range of1.05-1.50; gradually cooling the solution and allowing the solution tostand for a time sufficient to effect crystallization; and drying theresultant crystal suspension.
 15. A process in accordance with claim 14,wherein the solution is added with an effective amount of seed crystals.16. A process in accordance with claim 15, wherein the amount of seedcrystals is in the range of 0.1-20.0% relative to the dry solids.
 17. Aprocess in accordance with claim 15, wherein the solution is cooledunder stirring conditions.
 18. A process in accordance with claim 15,wherein the drying steps comprise:spray-drying the resultant crystalsuspension into powder; and aging the resultant crystalline powder in ahot air current.
 19. A process in accordance with claim 15, wherein thedrying steps comprise:allowing the resultant crystal suspension to standfor 0.5-5 days to solidify it into blocks; scraping the blocks intopowder; and drying the powder.
 20. A process in accordance with claim 1,wherein the maltitol incorporated into the foodstuff is wholecrystalline hydrogenated starch hydrolysate mixture solid containinganhydrous crystals of maltitol obtained by:providing a maltitol syrupwith a moisture content less than 5%; admixing an effective amount ofseed crystals to the syrup; kneading the resultant admixture at atemperature below the melting point of the crystals; and shaping theadmixture.
 21. A process in accordance with claim 14, wherein saidaqueous solution has been obtained by:catalytically hydrogenatingmaltose in aqueous solution; and purifying the hydrogenated solution.22. A solid foodstuff containing a substantially non-hydroscopic,free-flowing maltitol product selected from the group consisting ofanhydrous crystals of maltitol and whole crystalline hydrogenated starchhydrolysate mixture solid containing anhydrous crystals of maltitol. 23.A foodstuff in accordance with claim 22, wherein said foodstuff is infinely divided form.
 24. A foodstuff in accordance with claim 22,wherein said foodstuff is a sweetener.
 25. A foodstuff in accordancewith claim 22, wherein said foodstuff is a sweetened, low-caloricfoodstuff.
 26. A foodstuff in accordance with claim 22, wherein saidfoodstuff is a sweetened, low-cariogenic foodstuff.
 27. A foodstuff inaccordance with claim 22, wherein said maltitol product is anhydrouscrystals of maltitol obtained by:providing a 40°-95° C. aqueous solutionhaving a dry solids concentration of 65-95% by weight and a maltitolcontent of at least 65% based on the weight of the dry solids, whereinthe saturation degree of said aqueous solution is in the range of1.05-1.50; gradually cooling the solution and allowing the solution tostand for a time sufficient to effect crystallization; and recoveringanhydrous crystals of maltitol from the resultant crystal suspension.28. A foodstuff in accordance with claim 27, wherein the solution isadded with an effective amount of seed crystals.
 29. A foodstuff inaccordance with claim 28, wherein the amount of seed crystals is in therange of 0.1-20.0% relative to the dry solids.
 30. A foodstuff inaccordance with claim 28, wherein the solution is cooled under stirringconditions.
 31. A foodstuff in accordance with claim 28, wherein therecovering step comprises:separating the crystal suspension intoanhydrous crystals of maltitol and the mother liquor on a centrifuge;and washing the anhydrous crystals of maltitol with a minimum amount ofchilled water.
 32. A foodstuff in accordance with claim 28, wherein saidanhydrous crystals of maltitol are separated from the crystal suspensionwith a basket-type centrifuge.
 33. A foodstuff in accordance with claim27, wherein said aqueous solution has been obtained by:catalyticallyhydrogenating maltose in aqueous solution; and purifying thehydrogenated solution.
 34. A foodstuff in accordance with claim 22,wherein said maltitol product is whole crystalline hydrogenated starchhydrolysate mixture solid containing anhydrous crystals of maltitolobtained by:providing a 40-95° aqueous solution having a dry solidsconcentration of 65-95% by weight and a maltitol content of at least 65%by weight based on the weight of the dry solids, wherein the saturationdegree of said aqueous solution is in the range of 1.05-1.50; graduallycooling the solution and allowing the solution to stand for a timesufficient to effect crystallization; and drying the resultant crystalsuspension.
 35. A foodstuff in accordance with claim 34, wherein thesolution is added with an effective amount of seed crystals.
 36. Afoodstuff in accordance with claim 35, wherein the amount of seedcrystals is in the range of 0.1-20.0% relative to the dry solids.
 37. Afoodstuff in accordance with claim 35, wherein the solution is cooledunder stirring conditions.
 38. A foodstuff in accordance with claim 35,wherein the drying steps comprise:spray-drying the resultant crystalsuspension into powder; and aging the resultant crystalline powder in ahot air current.
 39. A foodstuff in accordance with claim 35, whereinthe drying steps comprise:allowing the resultant crystal suspension tostand for 0.5-5 days to solidify it into blocks; scraping the blocksinto powder; and drying the powder.
 40. A foodstuff in accordance withclaim 22, wherein said maltitol product is whole crystallinehydrogenated starch hydrolysate mixture solid containing anhydrouscrystals of maltitol obtained by:providing a maltitol syrup with amoisture content less than 5%; admixing an effective amount of seedcrystals to the syrup; kneading the resultant admixture at a temperaturebelow the melting point of the crystals; and shaping the admixture. 41.A foodstuff in accordance with claim 34, wherein said aqueous solutionhas been obtained by:catalytically hydrogenating maltose in aqueoussolution; and purifying the hydrogenated solution.